Battery Grade Lithium Research Articles

Optimization of resource recovery technologies in the disassembly of waste lithium batteries: A study on selective lithium extraction

This study focuses on optimizing resource recovery technology in the dismantling process of retired lithium batteries to mitigate environmental pollution. Addressing the challenge of significant precious metal losses in traditional hydrometallurgical recycling methods, this study employs a reductive roasting-carbonation leaching process to selectively extract lithium from cathode materials using a reducing agent. The study examines the effects of parameters such as roasting temperature, time, and reducing agent dosage on lithium leaching efficiency, and explores additional factors including carbonation leaching time, carbon dioxide flow rate, liquid-to-solid ratio, and leaching temperature in conjunction with multi-stage countercurrent leaching technology. Characterization of the roasting products and leaching process is performed using X-ray diffraction, scanning electron microscopy, and Fourier-transform infrared spectroscopy. The results demonstrate that, under conditions of a 700 °C roasting temperature, a 3-h roasting time, and a 15 % reducing agent dosage, the lithium leaching rate can achieve approximately 90 %. Following multi-stage countercurrent leaching, the lithium leaching rate exceeds 97 %, satisfying the purity requirements for battery-grade lithium carbonate. The innovation of this study is evident in its optimization of the recycling process, effectively separating and recovering cathode materials while reducing environmental pollution. This approach supports environmentally friendly waste treatment and contributes to the sustainable development of the battery industry.

Transformations of Critical Lithium Ores to Battery-Grade Materials: From Mine to Precursors

The escalating demand for lithium has intensified the need to process critical lithium ores into battery-grade materials efficiently. This review paper overviews the transformation processes and cost of converting critical lithium ores, primarily spodumene and brine, into high-purity battery-grade precursors. We systematically examine the study findings on various approaches for lithium recovery from spodumene and brine. Dense media separation (DMS) and froth flotation are the most often used processes for spodumene beneficiation. Magnetic separation (MS) and ore gravity concentration techniques in spodumene processing have also been considered. To produce battery-grade lithium salts, the beneficiated-concentrated spodumene must be treated further, with or without heat, in the presence of acidic or alkaline media. As a result, various pyro and hydrometallurgical techniques have been explored. Moreover, the process of extracting lithium from brine through precipitation, liquid–liquid extraction, and polymer inclusion membrane separation employing different organic, inorganic, and composite polymer sorbents has also been reviewed.

Lithium recovery from an alumina electrolysis slag leaching solution with strong acidity: Separation of lithium-ion and production of battery grade lithium carbonate

Lithium (Li) with excellent physicochemical properties is widely used in modern industries. However, the shortage and depletion of Li resources has hindered the sustainable economic development. Li recovery from waste resource was an effective approach, in particular, alumina electrolysis slag is exemplified as Li riched solid waste. In this work, separation of Li from alumina electrolysis slag leaching solution (AESLS) via solvent extraction using bis(2-ethylhexyl) hydrogen phosphate (P204) system was explored. Effects of saponification degree, phase ratio, and reaction time on metal ions impurities and Li extraction were investigated. Operational parameters including extraction, scrubbing, saponification and precipitation were optimized. Results showed that the extraction efficiencies of Mg2+, Ca2+, Al3+, Fe3+ and Li+ were 100 %, 100 %, 99.99 %, 100 % and 20.71 %, respectively, under the optimal single extraction conditions. The loss of Li after scrubbing of loaded organic phase using hydrochloric acid was as low as 1.59 %. The P204 extraction process was proved to be a thermodynamic process with spontaneous entropy increase, and the extraction order of metal ions was Al3+ > Fe3+ > Ca2+ > Mg2+ > Li+ according to the extraction driving force (ΔC); The solvent-extracted ligand mechanism was elucidated by infrared spectroscopy and nuclear magnetic resonance. Additionally, battery-grade lithium carbonate was produced. Our study paves a new way for recovery of Li in AESLS.

Selective recovery of lithium from used lithium-ion batteries spent via grain boundary reconstruction reaction

The demand for lithium resources on the market has increased significantly as a result of the emergence and advancement of the new energy industry. However, improper handling leads to the generation of large amounts of hazardous waste, including spent lithium batteries. The recovery of lithium from these batteries has dual importance in protecting the environment and effectively recycling secondary resources. Herein, a green process for selective extraction of lithium from discarded lithium batteries was proposed. Sodium thiosulfate mixed with waste lithium battery powder was calcined at 600 °C for 90 min, when the molar ratio of sodium thiosulfate to lithium in the raw material was 0.5, and over 99 % lithium can be selectively preferentially extracted. During the roasting process, lithium in the raw materials was converted into water-soluble LiNaSO4, and transition metal oxides after calcination existed as water-insoluble oxides or sulfides, and the goal of preferential lithium extraction can be achieved by simple immersion in water. Lithium-containing leachate was purified by cerium carbonate and NaOH. After removing a small amount of Ni, Co, Mn, Al, Ca, and F impurities, the prepared lithium carbonate had a purity greater than 99.50 %, which met the standard of battery-grade lithium carbonate. This study introduces an approach to the selective extraction of lithium from lithium-containing solid waste, which effectively simplifies the recycling separation procedure and provides support for resource utilization of lithium-containing solid waste.

Hybrid price prediction method combining TCN-BiGRU and attention mechanism for battery-grade lithium carbonate

Hybrid price prediction method combining TCN-BiGRU and attention mechanism for battery-grade lithium carbonate

Bringing the state back in the lithium triangle: An institutional analysis of resource nationalism in Chile, Argentina, and Bolivia

International efforts to tackle climate change have ignited a global surge in demand for the “critical metals” that are used in the production of lithium-ion batteries and electric vehicles (EVs). Among them, lithium represents a critical strategic component that is concentrated in only a limited number of extractive zones. In theory, limited availability and strong demand creates favourable conditions for producer states. In practice, many states have struggled to nationalize the production of battery-grade lithium, reflecting the dominant role that multinational corporations play in the sector. This paper explores the strategies that producer states in Chile, Argentina, and Bolivia have used to navigate this rapidly changing dynamic, making the case that the recent surge in demand for battery metals has created new opportunities for challenging the oligopoly of multinational capital but the ability of governments to reorient production linkages for enhancing incomes, technical capacity, and economic opportunity in the production of lithium derivatives remains structurally and historically constrained by the institutional legacies of nationalization and social mobilization that vary across the three states. Drawing upon the “political settlements” literature, we contend that national and subnational efforts to exert greater control over the lithium sector can be attributed to the institutional legacy of political contestation and the role of social actors in crafting new power configurations that challenge dominant state-business coalitions.

Environmental impacts of lithium supply chains from Australia to China

Abstract Lithium (Li) has been widely recognized as an essential metal for clean technologies. However, the environmental impacts and emission reduction pathways of the lithium supply chain haven’t been clearly investigated, especially between Australia and China, where most lithium ore are mined and produced. This study analyzed and compared the environmental and human health implications of six key cross-border Li supply chains from Australia to China through material flow analysis (MFA) and life cycle assessment (LCA) methods. Key findings include: (1) approximately 30% of total Li extraction is lost in the beneficiation stage due to low recovery rates; (2) the Cattlin-Yaan routes exhibit superior environmental and human health performances than other routes attributed to lower diesel consumption, reduced electricity use, and a high chemical conversion rate; (3) the Wodgina production routes have a higher carbon footprint mainly due to low ore grade and significant diesel consumption; (4) the dominant environmental implications in the supply chain are associated with refining battery-grade lithium carbonate, driven by energy use (electricity, coal and natural gas), sulfuric acid, soda ash, and sodium hydroxide. In addition, lithium carbonate refining has the highest water consumption. Overall, the analysis highlights opportunities to improve environmental performance, advance data-poor environmental assessments, and provide insights into sustainable Li extraction.

(Invited) Electroflow: Sustainable Electrochemical Lithium Chemical Production

The demand for lithium has soared in recent years as the adoption of electric vehicles has grown rapidly, and lithium supply will need to grow another ~5x from current day to meet projected demand for lithium in 2030. To keep pace with this exponentially growing demand, novel methods of lithium sourcing are needed. Direct lithium extraction (DLE) from saltwater brines holds promise to unlock the lithium resources needed to power the electric vehicle revolution.Lithium is traditionally sourced via two methods. Open pit hard rock mining is the method which many are familiar with. In this method, rocks are excavated, roasted with sulfuric acid, and the eluent is processed to produce a pure lithium product. This is well known to be environmentally destructive, and it produces larges amounts of waste products. The second method employed to produce lithium chemicals is brine evaporation ponds. In this method, brine is pumped to a surface pond, often multiple acres across, and solar evaporation concentrates the lithium in the brine to the point that it can undergo further processing. This method is extremely land and water intensive, and local residents adjacent to such ponds are increasingly worried about the effects of such methods on local water tables.Electroflow employs a DLE process to convert brine directly into pure, battery grade lithium chemicals via a sustainable electrochemical process. Our electrochemical cell design enables extraction from dilute lithium brine resources with as low as 10 ppm Li, which unlocks huge swaths of new lithium resources across the globe, and specifically in North America. We use lithium-selective electrode materials as the basis for lithium separation from brine solutions, and this allows a new paradigm of DLE processes that have not yet been thoroughly studied. This talk will describe the operation of our technology and explore the impact that it could have at scale.

Sustainable and efficient recovery of lithium from rubidium raffinate via solvent extraction

In recent years, with the increasing prevalence of rechargeable lithium-ion batteries in the burgeoning markets of electric vehicles and portable electronic devices, the consumption of lithium batteries has significantly surged. Hence, the efficient development and utilization of associated lithium resources bear paramount significance. This study aims to recover lithium from rubidium raffinate via solvent extraction. A systematic investigation was conducted to examine the effects of various parameters such as organic phase concentration, contact time, and phase ratio (O/A) during the separation process. The results indicated that the organic phase composed of 0.1 mol/L 4,4,4-Trifluoro-1-phenyl-1,3-butanedione (HBTA) and 0.1 mol/L Trioctylphosphine oxide (TOPO) could efficiently extract lithium from the rubidium raffinate. The optimal conditions were observed at a temperature of 20℃, O/A=1, and a contact time of 5 min. After three-stage countercurrent extraction, a lithium extraction rate of 99.24 % could be achieved, with over 95 % of the sodium easily scrubbed by 0.1 mol/L HCl at an O/A=10. With the use of 3 mol/L HCl, stripping efficiency exceeding 99 % could be attained at an O/A=10, consequently a successful preparation of battery-grade lithium carbonate product was achieved. Regeneration experiments confirmed the organic phase's excellent reproducibility efficiency. Slope analysis and density function theory (DFT) simulations indicated that optimal lithium extraction is achieved when HBTA and TOPO are at equal molar concentrations. The proposed process is expected to provide a green and sustainable route for the recovery of associated lithium resources.

Crystallization of battery-grade lithium carbonate with high recovery rate via solid-liquid reaction

Lithium carbonate (Li2CO3) stands as a pivotal raw material within the lithium-ion battery industry. Hereby, we propose a solid-liquid reaction crystallization method, employing powdered sodium carbonate instead of its solution, which minimizes the water introduction and markedly elevates one-step lithium recovery rate. Through kinetic calculations, the Li2CO3 solid-liquid reaction crystallization process conforms by the Avrami equation rather than shrinking core model, which means the dissolution rate of Na2CO3 is the most important factor affecting the reaction process. The effects of reaction conditions such as temperature and stirring speed on the Li2CO3 precipitation behavior were evaluated. The results indicated that temperature is a most essential parameter than other reaction conditions or stirring speed. The exceptional 93% recovery of Li2CO3 at 90 °C with a remarkable purity of 99.5% was achieved by using 1.2 M ratio of Na2CO3/Li2SO4. This method provides a new idea for the efficient preparation of battery-grade Li2CO3.

Carbon and water footprint of battery-grade lithium from brine and spodumene: A simulation-based LCA

Increasing demand for lithium driven by e-mobility spurs the expansion of lithium projects and exploration of lower-grade resources. This article combines process simulation (HSC Chemistry) and life cycle assessment tools to develop life cycle inventories considering declining ore grades scenarios for battery-grade Li2CO3 production from pivotal sources and regions (Salar de Atacama - brine and Greenbushes - spodumene). Depending on the ore grades, climate change results range from 5,0 to 25,0 kgCO2eq/kg Li2CO3 for brine and from 17,1 to 22,3 kgCO2eq/kg Li2CO3 for spodumene. Water consumption for brine varies from 0,2 to 7,7 m3/kg Li2CO3, depending on flow accounting, while for spodumene, it ranges from 0,2 to 0,5 m3/kg Li2CO3. The research shows that decreasing ore grade can lead to a fivefold increase in the carbon footprint for brine-based production and a 1.3-fold increase for spodumene. This underscores the importance of decarbonizing energy provision for lithium production to guarantee a sustainable battery supply chain. This research offers insights into using process simulation to enhance existing LCA studies in the raw materials industry and further develop inventory datasets, considering variations such as deposit ore grades.

Determination of trace anions in battery-grade lithium carbonate by double-inhibition on-line matrix-removal ion chromatography

A method was developed for the determination of trace anions in battery-grade lithium carbonate. In this method, lithium carbonate was dissolved in ultrapure water with ultrasound assistance, and its matrix was removed using an on-line matrix-removal method. In the matrix-removal process, the sample was first passed through an ADRS600(4 mm) suppressor (suppressor current, 150 mA; external water flow rate, 2 mL/min). Hydrogen and lithium ions were then completely exchanged via the ion-exchange membrane in the suppressor, converting the lithium carbonate into carbonic acid. The carbonic acid entered the waste-liquid channel in the form of carbon dioxide through a CRD 200(4 mm) carbonate removal device to remove the lithium carbonate matrix. Finally, the target anions were automatically enriched on an IonPac UTAC-LP2 concentration column (35 mm×3 mm) and automatically transferred to a chromatographic system using valve-switching technology. The chromatographic system featured an IonPac AG18 column (50 mm×2 mm) as the protection column and an IonPac AS18 column (250 mm×2 mm) as the analytical column. The column temperature was 30 ℃, gradient elution was performed using KOH solution as the eluent, and the pump flow rate was 0.30 mL/min. An ADRS600(2 mm) suppressor, suppressor current of 25 mA, injection volume of 250 μL, and conductance detector were also used. The results showed good linear relationships (r≥ 0.999) for F-, Cl-, [Formula: see text] in their respective concentration ranges. The limits of detection (LODs) and quantification (LOQs) were 0.05-0.88 and 0.15-2.92 μg/L, respectively. Lithium carbonate samples were tested six consecutive times, and the relative standard deviations (RSDs) of the peak areas of each ion were less than 0.73%. The same lithium carbonate samples were injected after 0, 2, 4, 8, 12, 18, and 24 h, and the RSD of the peak areas of each ion was less than 0.96%. The average recoveries ranged from 93.3% to 99.3%, and the RSDs (n=6) of samples spiked at three levels were in the range of 0.97%-3.45%. The proposed method has a low method limit of quantification of only 0.5 mg/kg for each ion analyzed and is capable of the simultaneous analysis of multiple ions. Thus, it is suitable for the detection of trace anions in battery-grade lithium carbonate.

Re-evaluation of battery-grade lithium purity toward sustainable batteries

Recently, the cost of lithium-ion batteries has risen as the price of lithium raw materials has soared and fluctuated. Notably, the highest cost of lithium production comes from the impurity elimination process to satisfy the battery-grade purity of over 99.5%. Consequently, re-evaluating the impact of purity becomes imperative for affordable lithium-ion batteries. In this study, we unveil that a 1% Mg impurity in the lithium precursor proves beneficial for both the lithium production process and the electrochemical performance of resulting cathodes. This is attributed to the increased nucleation seeds and unexpected site-selective doping effects. Moreover, when extended to an industrial scale, low-grade lithium is found to reduce production costs and CO2 emissions by up to 19.4% and 9.0%, respectively. This work offers valuable insights into the genuine sustainability of lithium-ion batteries.

A Green Method of Synthesizing Battery-Grade Lithium Sulfide: Hydrogen Reduction of Lithium Sulfate

A Green Method of Synthesizing Battery-Grade Lithium Sulfide: Hydrogen Reduction of Lithium Sulfate

Alkali-enhanced polyvinylidene fluoride cracking to deeply remove aluminum impurities for regeneration of battery-grade lithium iron phosphate

In the process of spent lithium iron phosphate resource recovery, a critical determinant in the extent of aluminum extraction is the presence of the binder. This binder encapsulates the aluminum foil, creating challenges in its removal and consequently hindering the attainment of battery-grade lithium iron phosphate (LFP) of the process. In this work, we implemented an alkali-enhanced PVDF cracking technique for efficient aluminum removal in spent LFP battery recycling. This innovative approach achieved a remarkable 98.6% aluminum removal rate, alongside a 97.8% lithium recovery rate, ensuring the production of battery-grade LFP. Notably, the recovered cathode material exhibited minimal alterations in chemical composition, crystal structure, and morphology. The results reveal that hydrogen generated during the alkali leaching reaction expands the interface between the aluminum foil and cathode material, enhancing the accessibility of OH– ions. These ions play a crucial role in decomposing the polyvinylidene fluoride (PVDF) binder and neutralizing the released HF. Moreover, OH– ions significantly aid in PVDF removal during calcination, facilitating deeper aluminum removal in subsequent processes. This research introduces a cost-effective, alkaline leaching-calcining process as a pre-treatment method for deep aluminum removal from spent cathode powders. This method not only removes impurity aluminum effectively but also ensures high lithium recovery, making the recycled product both battery-grade and economically viable at $6.06/Kg.

Selective recycling of lithium from spent LiNixCoyMn1-x-yO2 cathode via constructing a synergistic leaching environment

The global response to lithium scarcity is overstretched, and it is imperative to explore a green process to sustainably and selectively recover lithium from spent lithium-ion battery (LIB) cathodes. This work investigates the distinct leaching behaviors between lithium and transition metals in pure formic acid and the auxiliary effect of acetic acid as a solvent in the leaching reaction. A formic acid-acetic acid (FA-AA) synergistic system was constructed to selectively recycle 96.81% of lithium from spent LIB cathodes by regulating the conditions of the reaction environment to inhibit the leaching of non-target metals. Meanwhile, the transition metals generate carboxylate precipitates enriched in the leaching residue. The inhibition mechanism of manganese leaching by acetic acid and the leaching behavior of nickel or cobalt being precipitated after release was revealed by characterizations such as XPS, SEM, and FTIR. After the reaction, 90.50% of the acid can be recycled by distillation, and small amounts of the residual Li-containing concentrated solution are converted to battery-grade lithium carbonate by roasting and washing (91.62% recovery rate). This recycling process possesses four significant advantages: i) no additional chemicals are required, ii) the lithium sinking step is eliminated, iii) no waste liquid is discharged, and iv) there is the potential for profitability. Overall, this study provides a novel approach to the waste management technology of lithium batteries and sustainable recycling of lithium resources.

Artificial intelligence-enabled optimization of battery-grade lithium carbonate production

Employing AI to optimize the production of battery-grade lithium carbonate through a CO2-driven process, enhancing efficiency and reducing environmental impact of industrial Li production.

Application of Industrial-Scale Lithium Sulphate Electrolysis in Battery Recycling

As the world charges towards electrification and sustainable transportation, it is critical that the entire supply chain is equally sustainable. Industrial processes must be tailored towards circular processes in which emissions and effluents to the environment are minimized, if not eliminated altogether. When it comes to the production of battery grade lithium hydroxide monohydrate, a critical component of lithium ion batteries (LIBs), and the recovery of the lithium in spent LIBs. NORAM Electrolysis Systems Inc (NESI) has developed electrochemical technologies in which effluents are greatly reduced.NESI has developed a flexible, multi-compartment industrial electrolyser for salt splitting (NORSCAND®) applications including electrolysis of lithium sulphate to produce battery-grade lithium hydroxide (LHM). This electrolysis step can be used for the initial production of LHM or for recovering the LHM from recycling LIBs. In either case sulphuric acid is a by-product of the electrolysis process and it can then be recycled for dissolution of black mass in battery recycling processes or for e.g. SX regeneration. In both cases the incorporation of electrolysis in the flowsheet eliminates effluent streams.This presentation will outline the product quality and environmental benefits of electrolysis applied as part of a battery recycling flowsheet. It will outline the approach to electrolyser scale-up and present test and performance data from industrial-scale application. Figure 1

Battery Electrode-Based Lithium Recovery from Geothermal Brines

Driven by the electrification of transport sector the demand of lithium for battery application is increasing exponentially. The major sources for lithium are continental brines and hard minerals where the production comes along with consumptive water requirements and energy intensive processing and extraction. Therefore, it is of tremendous importance to consider alternative, non-conventional, sources and to develop more efficient and environmentally benign Li extraction methods. Geothermal brines can have significant Li concentrations (150–240 mgLi+ L−1)[1] and could represent an attractive sustainable lithium source. Implementing electrochemical methods for lithium extraction offers further advantages of high Li-selectivity, minimal waste production and low water consumption.[2] Here, we present a dual-ion battery type setup for the selective electrochemical Li-adsorption and desorption from geothermal brines. The chloride concentration in brines is a thousand times higher than that of Li+, hence, both species can be captured at opposite electrode sides. In the dual-ion setup presented in this work, Li+ are stored in a Li-selective LiFePO4(LFP) battery electrode and Cl− are stored using bismuth oxychloride (BiOCl) as counter electrode that has shown excellent Cl− storage capabilities and chemical stability in chloride-ion batteries and desalination batteries.[3] In the second step, both ions are released in a recovery solution to yield a Li-rich solution that could be further processed into battery-grade lithium hydroxide or carbonate. The stability of LFP in aqueous solutions and high Li -selectivity makes it a favored candidate for the electrochemical recovery of Li from natural solutions, where a diverse mixture of cations and anion is present.[4] Therefore, we examined the stability of the electrodes in brine solutions by XRD, indicating good reversibility and no intercalation of competitor ions. In addition, the Li-selectivity in extraction/recovery experiments was analyzed by ICP-OES and influences of different process parameters (e.g. current density, pH, temperature) were investigated. The results demonstrate that the LFP/BiOCl dual-ion battery setup is a feasible and promising low cost method for environmentally friendly Li extraction from geothermal brines.

Process intensification for the synthesis and purification of battery-grade Li2CO3 with microfluidics

Battery-grade lithium carbonate (Li2CO3) with a purity of higher than 99.5 wt% is of great importance as a high value-added lithium salt. However, influences of different reaction systems and process control on product purity remain unclear. Herein, a membrane dispersion microreactor was used to enhance the mass transfer of preparation and purification processes in homogeneous and heterogeneous system. Synthetic systems of Na2CO3–LiCl, NH4HCO3–LiCl, and NH3·H2O−CO2−LiCl, CO2 purification based on carbonation and decomposition were adopted. The Li2CO3 purity was increased by the improvement of mixing performance. The carbonation time was reduced by 62.5% and 58.3% for the NH3·H2O−CO2 and CO2 purification systems, respectively. In the two ammonia-based systems, Li2CO3 particles with a purity of 99.7–99.8 wt% were one-step prepared with a size of 3–5 μm, which also met the requirement of the battery-grade standard. The purity was further increased to 99.9 wt% by CO2 purification and LiHCO3 decomposition. The investigation could provide a feasible alternative for the controllable preparation of battery-grade Li2CO3 in one or multiple steps.